1. Field of the Invention
The field of art to which this invention pertains is molecular sieves. More specifically, the invention relates to phosphorus modified alumina molecular sieves comprising silicalite in a phosphorus modified alumina matrix and their method of manufacture.
2. Description of the Prior Art
It is well known in the separation art that certain crystalline aluminosilicates can be used to separate hydrocarbon types from mixtures thereof. As a few examples, a separation process disclosed in U.S. Pat. Nos. 2,985,589 and 3,201,491 uses a type A zeolite to separate normal paraffins from branched chain paraffins, and processes described in U.S. Pat. Nos. 3,265,750 and 3,510,423 use type X or type Y zeolites to separate olefinic hydrocarbons from paraffinic hydrocarbons. In addition to their use in processes for separating hydrocarbon types, X and Y zeolites have been employed in processes to separate individual hydrocarbon isomers. As a few examples, absorbents comprising X and Y zeolites are used in the process described in U.S. Pat. No. 3,114,782 to separate alkyl-trisubstituted benzene isomers; in the process described in U.S. Pat. No. 3,864,416 to separate alkyl-tetrasubstituted monocyclic aromatic isomers; and in the process described in U.S. Pat. No. 3,668,267 to separate specific alkyl-substituted naphthalenes. Because of the commercial importance of para-xylene, perhaps the more well known and extensively used hydrocarbon isomer separation processes are those for separating para-xylene from a mixture of C.sub.8 aromatics. In processes described in U.S. Pat. Nos. 3,558,730; 3,558,732; 3,626,020; 3,663,638; and 3,734,974, for example, molecular sieves comprising particular zeolites are used to separate para-xylene from feed mixtures comprising paraxylene and at least one other xylene isomer by selectively adsorbing para-xylene over the other xylene isomers.
In contrast, this invention relates to phosphorus modified alumina molecular sieves utilized for the separation of non-hydrocarbons and more specifically to the separation of fatty acids. Substantial uses of fatty acids are in the plasticizer and surface active agent fields. Derivatives of fatty acids are of value in compounding lubricating oil, as a lubricant for the textile and molding trade, in special lacquers, as a water-proofing agent, in the cosmetic and pharmaceutical fields, and in biodegradable detergents.
It is known from U.S. Pat. No. 4,048,205 to use type X and type Y zeolites for the separation of unsaturated from saturated esters of fatty acids. The type X and type Y zeolites, however, will not separate rosin acids found in tall oil from the fatty acids, apparently because the pore size of those zeolites (over 7 Angstroms) are large enough to accommodate and retain the relatively large diameter molecules of rosin acids as well as the smaller diameter molecules of fatty acids. Type A zeolite, on the other hand, has a pore size (about 5 Angstroms) which is unable to accommodate either of the above type acid and is, therefore unable to separate them. An additional problem when a zeolite is used to separate free acids is the reactivity between the zeolite and free acids.
It is also known that silicalite, a non-zeolitic hydrophobic crystalline silica molecular sieve, exhibits molecular sieve selectivity for a fatty acid with respect to a rosin acid, particularly when used with a specific displacement fluid. Silicalite. however, a fine powder, must be bound in some manner to enable its practical use as a molecular sieve. Most binders heretofore attempted are not suitable for use in separating the components of tall oil because of the binder's reactivity or interference with the separation. One binder that has been found effective is amorphous silica, which. however, must be treated in some manner to eliminate hydroxyl groups on the molecular sieve particles.
We have discovered a new binder which when incorporated with the silicalite provides a new molecular sieve uniquely suitable for the separation of the components of tall oil.